arXiv subjects

Daniel M. Reich

Publications and source records attributed to Daniel M. Reich.

At least 19 recordsLinked to original sources

arXiv2026

Elucidating the Control of Circular Dichroism in Ion Yield via Chirped Pulses with Purposeful Models

We theoretically investigate circular dichroism in the ion yield following $1+1+1$ ionization of 3-methylcyclopentanone using femtosecond linearly chirped laser pulses, inspired by recent experiments by Das et al. [Phys. Chem. Chem. Phys. 27, 8043 (2025)]. To this end, we numerically solve the time-dependent Schr\"odinger equation and evaluate the total population in the Rydberg states at the end of the second absorption step. The A-band transition in the first absorption step is treated using state-of-the-art quantum-chemical calculations, whereas the second absorption step is described via an effective model. Within our framework, we identify the interplay between the first and second absorption step as the key explanation for the experimentally observed chirp dependence of the anisotropy. By elucidating this mechanism for the chirp-enhanced signal, our findings contribute towards the development of improved control schemes for chiral molecules.

physics.atom-ph↗

arXiv2025

Reconstructing the unitary part of a noisy quantum channel

We consider the problem of reconstructing the unitary describing the evolution of a quantum system, or quantum channel, from a set of input and output states. For ideal, fully coherent evolution, we show that the unitary can be reconstructed from two mixed states or $d+1$ pure states, where $d$ is the size of Hilbert space. The reconstruction method can be extended to approximate the unitary part of a dynamical map, provided the decoherence is not too strong to render this question meaningless. We exemplify the method for the example of the cross-resonance gate as well as a random set of unitaries, comparing the reconstruction from pure, respectively mixed, states to an approach based on the Choi matrix. We find that the pure state reconstruction requires the least amount of resources when the dynamics is close to unitary, whereas the mixed state approach outperforms the pure state reconstruction in terms of channel uses for appreciable decoherence. These conclusions hold also in the presence of SPAM errors and irrespective of the Hilbert space size.

quant-ph↗

arXiv2024

Feshbach Resonances in Cold Collisions: Benchmarking State of the Art ab initio Potential Energy Surfaces

High-quality potential energy surfaces (PES) are a prerequisite for quantitative atomistic simulations, with both quantum and classical dynamics approaches. The ultimate test for the validity of a PES are comparisons with judiciously chosen experimental observables. Here we ask whether cold collision measurements are sufficiently informative to validate and distinguish between high-level, state-of-the art PESs for the strongly interacting Ne-H$_2^+$ system. We show that measurement of the final state distributions for a process that involves only several metastable intermediate states is sufficient to identify the PES that captures the long-range interactions properly. Furthermore, we show that a modest increase in the experimental energy resolution will allow for resolving individual Feshbach resonances and enable a quantitative probe of the interactions at short and intermediate range.

physics.chem-ph↗

arXiv2024

Numerical evaluation of orientation averages and its application to molecular physics

In molecular physics, it is often necessary to average over the orientation of molecules when calculating observables, in particular when modelling experiments in the liquid or gas phase. Evaluated in terms of Euler angles, this is closely related to integration over two- or three-dimensional unit spheres, a common problem discussed in numerical analysis. The computational cost of the integration depends significantly on the quadrature method, making the selection of an appropriate method crucial for the feasibility of simulations. After reviewing several classes of spherical quadrature methods in terms of their efficiency and error distribution, we derive guidelines for choosing the best quadrature method for orientation averages and illustrate these with three examples from chiral molecule physics. While Gauss quadratures allow for achieving numerically exact integration for a wide range of applications, other methods offer advantages in specific circumstances. Our guidelines can also by applied to higher-dimensional spherical domains and other geometries. We also present a Python package providing a flexible interface to a variety of quadrature methods.

physics.comp-ph↗

arXiv2024

Tracking chirality in photoelectron circular dichroism

In photoelectron circular dichroism (PECD) it is generally difficult to trace how and when the chirality of the molecule is imprinted onto the photoelectron. We present simulations of PECD in a simple model and employ chirality measures to establish a quantitative connection between the chirality of the potential, the electronic wave function's chirality, and the anisotropy of the photoelectron distribution. We show that these measures are suitable indicators for chirality, paving the way for tracking the chiral evolution from the nuclear scaffold to the final observable.

physics.atom-ph↗

arXiv2024

Anisotropy factor spectra for weakly allowed electronic transitions in chiral ketones

Quantum chemical calculations of one-photon absorption, electronic circular dichroism and anisotropy factor spectra for the A-band transition of fenchone, camphor and 3-methylcyclopentanone (3MCP) are reported. While the only weakly allowed nature of the transition leads to comparatively large anisotropies, a proper theoretical description of the absorption for such a transition requires to account for non-Condon effects. We present experimental data for the anisotropy of 3MCP in the liquid phase and show that corresponding Herzberg-Teller corrections are critical to reproduce the main experimental features. The results obtained with our comprehensive theoretical model highlight the importance of the vibrational degree of freedom, paving the way for a deeper understanding of the dynamics in electronic circular dichroism.

physics.chem-ph↗

arXiv2023

Determining the ability for universal quantum computing: Testing controllability via dimensional expressivity

Operator controllability refers to the ability to implement an arbitrary unitary in SU(N) and is a prerequisite for universal quantum computing. Controllability tests can be used in the design of quantum devices to reduce the number of external controls. Their practical use is hampered, however, by the exponential scaling of their numerical effort with the number of qubits. Here, we devise a hybrid quantum-classical algorithm based on a parametrized quantum circuit. We show that controllability is linked to the number of independent parameters, which can be obtained by dimensional expressivity analysis. We exemplify the application of the algorithm to qubit arrays with nearest-neighbour couplings and local controls. Our work provides a systematic approach to the resource-efficient design of quantum chips.

quant-ph↗

arXiv2023

Optimizing for an arbitrary Schrödinger cat state. II. Application in the presence of dissipation

We extend here the optimization functional targeting arbitrary cat states, derived in the companion paper, to open quantum system dynamics. Applying it to a Jaynes-Cummings model with decay on the oscillator, we find, for strong dissipation and large cat radii, a change in the control strategy for preparing an entangled cat state. Our results illustrate the versatility of the quantum optimal control toolbox for practical applications in the quantum technologies.

quant-ph↗

arXiv2023

Optimizing for an arbitrary Schrödinger cat state

We derive a set of functionals for optimization towards an arbitrary cat state and demonstrate their application by optimizing the dynamics of a Kerr-nonlinear Hamiltonian with two-photon driving. The versatility of our framework allows us to adapt our functional towards optimization of maximally entangled cat states, applying it to a Jaynes-Cummings model. We identify the strategy of the obtained control fields and determine the quantum speed limit as a function of the cat state's excitation. Finally, we extend our optimization functionals to open quantum system dynamics and apply it to the Jaynes-Cummings model with decay on the oscillator. For strong dissipation and large cat radii, we find a change in the control strategy compared to the case without dissipation. Our results highlight the power of optimal control with functionals specifically crafted for complex physical tasks and the versatility of the quantum optimal control toolbox for practical applications in the quantum technologies.

quant-ph↗

arXiv2023

Tomography of Feshbach Resonance States

Feshbach resonances are fundamental to interparticle interactions and become particularly important in cold collisions with atoms, ions, and molecules. Here we present the detection of Feshbach resonances in a benchmark system for strongly interacting and highly anisotropic collisions -- molecular hydrogen ions colliding with noble gas atoms. The collisions are launched by cold Penning ionization exclusively populating Feshbach resonances that span both short- and long-range parts of the interaction potential. We resolved all final molecular channels in a tomographic manner using ion-electron coincidence detection. We demonstrate the non-statistical nature of the final state distribution. By performing quantum scattering calculations on ab initio potential energy surfaces, we show that the isolation of the Feshbach resonance pathways reveals their distinctive fingerprints in the collision outcome.

physics.atom-ph↗

arXiv2022

Increasing ion yield circular dichroism in femtosecond photoionisation using optimal control theory

We investigate how optimal control theory can be used to improve Circular Dichroism (CD) signals for A--band of fenchone measured via the photoionization yield upon further excitation. These transitions are electric dipole forbidden to first order, which translates into low population transfer to the excited state (~8%) but also allows for a clearer interplay between electric and magnetic transition dipole moments, which are of the same order of magnitude. Using a model including the electronic ground and excited A state as well as all permanent and transition multipole moments up to the electric quadrupole, we find that the absolute CD signal of randomly oriented molecules can be increased by a factor 3.5 when using shaped laser pulses, with the anisotropy parameter g increasing from 0.06 to 1. Our insights provide additional evidence on how optimal control can assist in amplifying chiral signatures via interactions of permanent and transition multipole moments.

physics.chem-ph↗

arXiv2021

Coherent Control of Ultrafast Bond Making and Subsequent Molecular Dynamics: Demonstration of Final-State Branching Ratio Control

Quantum coherent control of ultrafast bond making and the subsequent molecular dynamics is crucial for the realization of a new photochemistry, where a shaped laser field is actively driving the chemical system in a coherent way from the thermal initial state of the reactants to the final state of the desired products. We demonstrate here coherent control over the relative yields of Mg$_2$ molecules that are generated via photoassociation and subsequently photodriven into different groups of final states. The strong-field process involves non-resonant multiphoton femtosecond photoassociation of a pair of thermally hot magnesium atoms into a bound Mg$_{2}$ molecule and subsequent molecular dynamics on electronically excited states. The branching-ratio control is achieved with linearly chirped laser pulses, utilizing the different chirp dependence that various groups of final molecular states display for their post-pulse population. Our study establishes the feasibility of high degree coherent control over quantum molecular dynamics that is initiated by femtosecond photoassociation of thermal atoms.

physics.atom-ph↗

arXiv2021

Optimal control theory for a unitary operation under dissipative evolution

We show that optimizing a quantum gate for an open quantum system requires the time evolution of only three states irrespective of the dimension of Hilbert space. This represents a significant reduction in computational resources compared to the complete basis of Liouville space that is commonly believed necessary for this task. The reduction is based on two observations: The target is not a general dynamical map but a unitary operation; and the time evolution of two properly chosen states is sufficient to distinguish any two unitaries. We illustrate gate optimization employing a reduced set of states for a controlled phasegate with trapped atoms as qubit carriers and a $\sqrt{i\text{SWAP}}$ gate with superconducting qubits.

quant-ph↗

arXiv2020

Determining the nature of quantum resonances by probing elastic and reactive scattering in cold collisions

Scattering resonances play a central role in collision processes in physics and chemistry. They help building an intuitive understanding of the collision dynamics due to the spatial localization of the scattering wavefunctions. For resonances that are localized in the reaction region, located at short separation behind the centrifugal barrier, sharp peaks in the reaction rates are the characteristic signature, observed recently with state-of-the-art experiments in low energy collisions. If, however, the localization occurs outside of the reaction region, mostly the elastic scattering is modified. This may occur due to above barrier resonances, the quantum analogue of classical orbiting. By probing both elastic and inelastic scattering of metastable helium with deuterium molecules in merged beam experiments, we differentiate between the nature of quantum resonances -- tunneling vs above barrier -- and corroborate our findings by calculating the corresponding scattering wavefunctions.

physics.chem-ph↗

arXiv2020

Fundamental Bounds on Qubit Reset

Qubit reset is a basic prerequisite for operating quantum devices, requiring the export of entropy. The fastest and most accurate way to reset a qubit is obtained by coupling the qubit to an ancilla on demand. Here, we derive fundamental bounds on qubit reset in terms of maximum fidelity and minimum time, assuming control over the qubit and no control over the ancilla. Using the Cartan decomposition of the Lie algebra of qubit plus two-level ancilla, we identify the types of interaction and controls for which the qubit can be purified. For these configurations, we show that a time-optimal protocol consists of purity exchange between qubit and ancilla brought into resonance, where the maximum fidelity is identical for all cases but the minimum time depends on the type of interaction and control. Furthermore, we find the maximally achievable fidelity to increase with the size of the ancilla Hilbert space, whereas the reset time remains constant.

quant-ph↗

arXiv2019

Krotov: A Python implementation of Krotov's method for quantum optimal control

We present a new open-source Python package, krotov, implementing the quantum optimal control method of that name. It allows to determine time-dependent external fields for a wide range of quantum control problems, including state-to-state transfer, quantum gate implementation and optimization towards an arbitrary perfect entangler. Krotov's method compares to other gradient-based optimization methods such as gradient-ascent and guarantees monotonic convergence for approximately time-continuous control fields. The user-friendly interface allows for combination with other Python packages, and thus high-level customization. The package is being developed at https://github.com/qucontrol/krotov

quant-ph↗

arXiv2019

Optimized Sampling of Mixed-State Observables

Quantum dynamical simulations of statistical ensembles pose a significant computational challenge due to the fact that mixed states need to be represented. If the underlying dynamics is fully unitary, for example in ultrafast coherent control at finite temperatures, one approach to approximate time-dependent observables is to sample the density operator by solving the Schrödinger equation for a set of wave functions with randomized phases. We show that, on average, random-phase wave functions perform well for ensembles with high mixedness, whereas at higher purities a deterministic sampling of the energetically lowest-lying eigenstates becomes superior. We prove that minimization of the worst-case error for computing arbitrary observables is uniquely attained by eigenstate-based sampling. We show that this error can be used to form a qualitative estimate of the set of ensemble purities for which the sampling performance of the eigenstate-based approach is superior to random-phase wave functions. Furthermore we present refinements to both schemes which remove redundant information from the sampling procedure to accelerate their convergence. Finally, we point out how the structure of low-rank observables can be exploited to further improve eigenstate-based sampling schemes.

quant-ph↗

arXiv2019

Phase protection of Fano-Feshbach resonances

Decay of bound states due to coupling with free particle states is a general phenomenon occurring at energy scales from MeV in nuclear physics to peV in ultracold atomic gases. Such a coupling gives rise to Fano-Feshbach resonances (FFR) that have become key to understanding and controlling interactions - in ultracold atomic gases, but also between quasiparticles such as microcavity polaritons. The energy positions of FFR were shown to follow quantum chaotic statistics. In contrast, lifetimes which are the fundamental property of a decaying state, have so far escaped a similarly comprehensive understanding. Here we show that a bound state, despite being resonantly coupled to a scattering state, becomes protected from decay whenever the relative phase is a multiple of $π$. We observe this phenomenon by measuring lifetimes spanning four orders of magnitude for FFR of spin-orbit excited molecular ions with merged beam and electrostatic trap experiments. Our results provide a blueprint for identifying naturally long-lived states in a decaying quantum system.

physics.atom-ph↗